Polyorganosiloxanes

Abstract

The polyorganosiloxane according to the present invention has a structure represented by formula (1). (In formula (1), each R1 independently represents a group represented by A-B or a monovalent hydrocarbon group having 1-4 carbon atoms, at least one of the plurality of R1 represents a group represented by A-B, A represents a divalent organic group bonded to a silicon atom, B has a conjugated 3-6 aromatic 6-membered ring, and among the atoms constituting the A, R1 represents a hydrogen atom, and R2 represents a hydrogen atom; if an atom bonded to the aromatic ring of B is an alpha-site atom, an atom bonded to the alpha-site atom is a beta-site atom, and an atom bonded to the beta-site atom and an atom other than the alpha-site atom are a gamma-site atom, any one of the alpha-site atom, the beta-site atom, and the gamma-site atom is a heteroatom. And n is an integer of 1 or more. ) According to the present invention, it is possible to provide a polyorganosiloxane having improved dispersibility by improving the adsorbability to a filler, and having high flowability. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a polyorganosiloxane suitable for use as a dispersant for fillers. Background Art

[0002] In recent years, due to the increasing heat generation accompanying the high integration of circuits in electronic devices, thermal countermeasures have become important, and thus the demand for heat dissipation materials has increased. For example, for high heat dissipation, heat dissipation materials using fillers such as graphite are known.

[0003] Generally, fillers have poor dispersibility in solvents, and in particular, graphite, which is a compound having a π-conjugated system, has poor dispersibility, and improvement is required from the viewpoint of improving heat dissipation.

[0004] As a dispersant for improving the dispersibility of fillers, a compound composed of a part interacting with the filler (filler linking group) and a polymer main chain is known.

[0005] In Patent Document 1, a polycyclic aromatic group mono-terminal polyorganosiloxane having an aromatic condensed ring group was disclosed as a treatment agent for improving the dispersibility of nano-carbon. Further, in the examples, specifically, an example of using a polyorganosiloxane having a pyrene group as the aromatic condensed ring group was shown. It is considered that this polyorganosiloxane can improve the dispersibility by utilizing the π-π interaction with nano-carbon due to having an aromatic condensed ring group.

[0006] In Patent Document 2, a specific polyorganosiloxane having a monovalent hydrocarbon group having 10 or more carbon atoms and having a plurality of aromatic rings was disclosed, and it was described that this polyorganosiloxane is useful as a surface treatment agent for various functional filler materials, does not impair the operability and dispersion stability of various functional filler materials, and can be mixed in a large amount in a resin composition.

[0007] Prior Art Documents

[0008] Patent Documents

[0009] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2018-197300

[0010] Patent Document 2: Japanese Translation of PCT International Application Publication No. 2016-534161 Summary of the Invention

[0011] Problems to be Solved by the Invention

[0012] However, since the polyorganosiloxane described in Patent Document 1 has low fluidity in a solvent, when used as a treatment agent, heating or ultrasonic treatment is sometimes required, and the operation efficiency deteriorates.

[0013] In Patent Document 2, although a polyorganosiloxane having a plurality of aromatic rings is described, sometimes the affinity with a filler is low, and sometimes the filler cannot be sufficiently dispersed in a solvent.

[0014] Therefore, an object of the present invention is to provide a polyorganosiloxane that improves the adsorptivity to a filler to improve dispersibility and has high fluidity.

[0015] Means for Solving the Problem

[0016] The inventors of the present invention repeatedly conducted in-depth studies to achieve the above object, and as a result, found that the above problem can be solved by a polyorganosiloxane having 3 or more and 6 or less conjugated aromatic 6-membered rings and having a heteroatom at a specific position, thereby completing the present invention.

[0017] That is, the present invention relates to the following [1] to [8].

[0018] [1] A polyorganosiloxane having a structure represented by the following formula (1).

[0019]

[0020] (In formula (1), each R1 is independently a group represented by A-B or a monovalent hydrocarbon group having 1 to 4 carbon atoms,

[0021] at least one of the plurality of R1s is a group represented by A-B, A is a divalent organic group bonded to a silicon atom, and B has 3 or more and 6 or less conjugated aromatic 6-membered rings,

[0022] among the atoms constituting A, the atom bonded to the aromatic 6-membered ring of B is defined as an α-position atom, the atom bonded to the α-position atom is defined as a β-position atom, and when the atom bonded to the β-position atom and other than the α-position atom is defined as a γ-position atom, any one of the α-position atom, the β-position atom, and the γ-position atom is a heteroatom,

[0023] n is an integer of 1 or more.)

[0024] [2] The polyorganosiloxane according to the above [1], having a structure represented by the following formula (2).

[0025]

[0026] (In formula (2), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and A, B, and n have the same meanings as A, B, and n in formula (1).)

[0027] [3] The polyorganosiloxane according to the above [1], having a structure represented by the following formula (3).

[0028]

[0029] (In formula (3), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and A, B, and n have the same meanings as A, B, and n in formula (1).)

[0030] [4] The polyorganosiloxane according to the above [1] has a structure represented by the following formula (4).

[0031]

[0032] (In formula (4), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, m is an integer of 1 or more and 10 or less, and A, B, and n have the same meanings as A, B, and n in formula (1).)

[0033] [5] In the polyorganosiloxane according to the above [4], m is 1 or 2.

[0034] [6] In the polyorganosiloxane according to any one of the above [1] to [5], B is a polycyclic compound.

[0035] [7] In the polyorganosiloxane according to any one of the above [1] to [6], B contains a pyrene substituent or a perylene substituent.

[0036] [8] In the polyorganosiloxane according to any one of the above [1] to [7], the number of carbon atoms of A is 10 or less.

[0037] Effects of the Invention

[0038] According to the present invention, a polyorganosiloxane can be provided which has improved adsorptivity to a filler, thereby improving dispersibility and having high fluidity. Detailed Description of the Invention

[0039] [Polyorganosiloxane]

[0040] The polyorganosiloxane of the present invention has a structure represented by the following formula (1).

[0041]

[0042] (In formula (1), each R1 is independently a group represented by A-B or a monovalent hydrocarbon group having 1 to 4 carbon atoms,

[0043] at least one of the plurality of R1s is a group represented by A-B, A is a divalent organic group bonded to the silicon atom of formula (1), and B has 3 or more and 6 or less conjugated aromatic 6-membered rings,

[0044] Among the atoms constituting the above A, when the atom bonded to the aromatic six-membered ring of the above B is defined as the α-position atom, the atom bonded to the α-position atom is defined as the β-position atom, and the atom bonded to the β-position atom and other than the α-position atom is defined as the γ-position atom, any one of the α-position atom, β-position atom, and γ-position atom is a heteroatom,

[0045] n is an integer of 1 or more.)

[0046] The inventors of the present invention studied the dispersibility of polyorganosiloxane used as a dispersant in a solvent. It is known that the conventional polyorganosiloxane described in Patent Document 1 has an aryl group with a large conjugated system and high crystallinity such as a pyrene group introduced, so the adsorptivity of the dispersant to the filler can be improved, but the fluidity of the dispersant is reduced and the diffusibility in the solvent is poor. Therefore, when used as a treatment agent, heating or ultrasonic treatment is sometimes required, and the operation efficiency is likely to deteriorate.

[0047] On the other hand, in order to improve the diffusibility of the polyorganosiloxane used as a dispersant in a solvent, it is possible to consider improving the fluidity of the dispersant itself. For example, by introducing an aryl group with a small conjugated system and low crystallinity such as a naphthalene skeleton, the fluidity of the dispersant can be improved. In this case, since the conjugated system of the aryl group is small, the interaction with the filler becomes small, and the adsorptivity of the dispersant to the filler becomes low. As a result, a sufficient effect of improving the dispersibility of the filler cannot be obtained. That is, at present, a dispersant that improves the dispersibility of the filler and has high fluidity has not been obtained.

[0048] A polyorganosiloxane having a plurality of aromatic rings as described in Patent Document 2 is also known, but in this case, since the conjugated system of the aryl group is small, the adsorptivity of the dispersant to the filler is poor. Therefore, the filler cannot sometimes be sufficiently dispersed in the solvent. There is no description or suggestion in Patent Document 2 regarding the specific structure for obtaining a dispersant having a large conjugated system aryl group and high fluidity.

[0049] The polyorganosiloxane of the present invention can provide a polyorganosiloxane that improves the adsorptivity to the filler to improve the dispersibility and has high fluidity. The reason is uncertain, but it is presumed as follows.

[0050] The polyorganosiloxane of the present invention has 3 or more and 6 or less conjugated aromatic 6-membered rings and has a portion with a large conjugated system in its molecular structure. Therefore, the polyorganosiloxane of the present invention has a high adsorption property to fillers, particularly fillers having a π-conjugated system structure, through π-π interaction, and thus it is easy to disperse the fillers. Further, any one of the α-position atom, β-position atom, and γ-position atom bonded to the aromatic 6-membered ring of the polyorganosiloxane of the present invention is a heteroatom. It is considered that if there are only C-C bonds near the aromatic ring, the degree of freedom of bond rotation is low, the configuration near the aromatic ring is fixed, and the crystallinity increases, resulting in a decrease in fluidity. However, the degree of freedom of rotation increases due to the presence of a heteroatom near the aromatic ring, and various configurations can be adopted near the aromatic ring, resulting in a decrease in crystallinity and an increase in fluidity.

[0051] <Polyorganosiloxane represented by Formula (1)>

[0052] In Formula (1), each R1 is independently a group represented by A-B or a monovalent hydrocarbon group having 1 to 4 carbon atoms.

[0053] At least one of the plurality of R1s is a group represented by A-B. A is a divalent organic group and is bonded to the silicon atom of Formula (1).

[0054] Among the atoms constituting A, any one of the α-position atom, β-position atom, and γ-position atom is a heteroatom. Thereby, the fluidity of the polyorganosiloxane is improved. From the viewpoint of improving the fluidity of the polyorganosiloxane, it is preferred that the α-position atom or the β-position atom is a heteroatom, and more preferably the α-position atom is a heteroatom.

[0055] Here, the α-position atom is an atom among the atoms constituting the above A that is bonded to the aromatic 6-membered ring (i.e., one of the conjugated 3 or more and 6 or less aromatic 6-membered rings possessed by B) possessed by the above B. The β-position atom is an atom among the atoms constituting A that is bonded to the above α-position atom. The γ-position atom is an atom other than the α-position atom that is bonded to the β-position atom.

[0056] In addition, A may also have a heteroatom in a portion other than the α-position atom, β-position atom, and γ-position atom.

[0057] The heteroatom is not particularly limited, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, a boron atom, etc. Among them, from the viewpoint of effectively improving the fluidity of the polyorganosiloxane, an oxygen atom is preferred.

[0058] A is preferably a divalent organic group having 11 or less carbon atoms, more preferably a divalent organic group having 10 or less carbon atoms. Thus, a polyorganosiloxane in which the number of carbon atoms of A is a certain amount or less is likely to improve the dispersibility of the filler in the solvent, which is preferred. In addition, the lower limit of the number of carbon atoms of A is not particularly limited, but A is preferably a divalent organic group having 4 or more carbon atoms.

[0059] Since A has a heteroatom as described above, it has a structural unit having a heteroatom. As such a structural unit, for example, an ether, an ester, an amide, a urethane, a thioether, a thioester, etc. can be cited. Among them, from the viewpoints of improving the dispersibility of the filler and improving the fluidity, an ether or an ester is preferred, an ether is more preferred, and a cyclic ether is particularly preferred. In addition, a cyclic ether is an ether having a structure in which the carbon of the cyclic hydrocarbon is replaced by oxygen.

[0060] In addition, from the viewpoints of improving the dispersibility of the filler and improving the fluidity, A preferably has a skeleton represented by the following formula (5-1) or formula (5-2).

[0061]

[0062] In formula (5-1), *1 and *2 are bonding bonds, R4 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom. Two R4s may be the same or different. R3 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrocarbon group having 1 to 4 carbon atoms, more preferably a hydrocarbon group having 1 to 3 carbon atoms, and further preferably an ethyl group. R5 is a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms, preferably a hydrogen atom. The oxygen atom in formula (5-1) is the above-mentioned β-position atom or γ-position atom, preferably the β-position atom.

[0063] In formula (5-2), *3 and *4 are bonding bonds. The oxygen atom having the bonding bond of *3 is the above-mentioned α-position atom, β-position atom or γ-position atom.

[0064] Among the above, A preferably has a skeleton represented by formula (5-1).

[0065] Furthermore, from the viewpoints of improving the dispersibility of the filler and improving the fluidity, A is preferably any one of the structures represented by the following formula (6) to formula (10).

[0066]

[0067] In formula (6) to formula (10), *5 is a bonding bond that binds to the aromatic 6-membered ring possessed by B, and *6 is a bonding bond that binds to the silicon atom of formula (1).

[0068] B in formula (1) has 3 or more and 6 or less conjugated aromatic 6-membered rings. By "conjugated" is meant that unsaturated bonds and single bonds are alternately connected in the molecular structure, resulting in stabilization through the interaction of p-orbitals and delocalization of electrons (existing over the entire conjugated system).

[0069] If the number of aromatic 6-membered rings is 7 or more, the fluidity of the polyorganosiloxane deteriorates. If the number of aromatic 6-membered rings is 2 or less, the adsorptivity to the filler decreases and the dispersibility of the filler becomes poor.

[0070] From the viewpoint of improving both the adsorptivity to the filler and the fluidity well in balance, the number of aromatic 6-membered rings is preferably 4 or more and 5 or less.

[0071] The 3 or more and 6 or less conjugated aromatic 6-membered rings can be a condensed ring compound composed of 3 or more and 6 or less aromatic 6-membered rings, or a non-condensed ring compound, but a condensed ring compound is preferred. Thus, when B contains a condensed ring compound or B is a condensed ring compound, the adsorptivity to the filler is further improved, which is preferred from the viewpoint of improving dispersibility.

[0072] Examples of the above-mentioned condensed ring compounds include anthracene substituents, phenanthrene substituents, benzo[9,10]phenanthrene substituents, pyrene substituents, tetracene substituents, picene substituents, perylene substituents, pentaphene substituents, pentacene substituents, or hexaphene substituents, etc. Among them, pyrene substituents or perylene substituents are preferred. Here, by "substituent" is meant that it can have a substituent. For example, by "anthracene substituent" is meant that it includes both anthracene and anthracene having a substituent, and the same applies to other substituents.

[0073] When the above-mentioned condensed ring compound has a substituent, at least 1 or more of the hydrogen atoms constituting the condensed ring compound are substituted by a substituent. Examples of the substituent include organic groups having 1 to 10 carbon atoms.

[0074] From the viewpoint of improving the fluidity of the polyorganosiloxane of the present invention, the above-mentioned condensed ring compound preferably does not have a substituent. Therefore, B is particularly preferably pyrene or perylene.

[0075] In addition, for the above-mentioned condensed ring compound, any carbon atom constituting the condensed ring may be bonded to the above-mentioned A.

[0076] In the present invention, B can be used without particular limitation as described above, but the following shows the preferred structure of B.

[0077]

[0078] In the above formulas (11) to (14), * is a bonding bond bonded to A.

[0079] Among the above formulas (11) to (14), any compound of formulas (11) to (13) as polycyclic compounds is preferred, among which pyrene of formula (11) or perylene of formula (12) is more preferred, and perylene of formula (12) is further preferred.

[0080] In formula (1), at least one R1 is the group represented by A-B above, and the remaining R1s are hydrocarbon groups having 1 to 4 carbon atoms. In formula (1), among multiple R1s, the number of the groups represented by A-B is preferably 1 or more and 5 or less, more preferably 1 or 2, and the remaining are preferably monovalent hydrocarbon groups having 1 to 4 carbon atoms. When there are multiple groups represented by A-B, these multiple groups represented by A-B may be the same or different.

[0081] Examples of the monovalent hydrocarbon group having 1 to 4 carbon atoms include, for example, methyl, ethyl, propyl, butyl, etc., and among them, methyl is preferred. When there are multiple monovalent hydrocarbon groups having 1 to 4 carbon atoms, these multiple monovalent hydrocarbon groups having 1 to 4 carbon atoms may be the same or different.

[0082] In formula (1), n represents the repetition number, and n is an integer of 1 or more. As long as n is an integer of 1 or more, there is no particular limitation, but from the viewpoint of good fluidity, it is preferably 500 or less, more preferably 300 or less, further preferably 250 or less, still further preferably 20 or more, more preferably 100 or more, and further preferably 200 or more.

[0083] The polyorganosiloxane having the structure represented by formula (1) may have the group represented by A-B at a single terminal, may have the group represented by A-B at both terminals, may have the group represented by A-B in the side chain, may have the group represented by A-B at a single terminal and in the side chain, or may have the group represented by A-B at both terminals and in the side chain.

[0084] <Polyorganosiloxane represented by formula (2)>

[0085] The polyorganosiloxane according to an embodiment of the present invention has the structure represented by the following formula (2). This polyorganosiloxane has the group represented by A-B at a single terminal.

[0086]

[0087] (In formula (2), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and A, B, and n have the same meanings as A, B, and n in formula (1).)

[0088] In formula (2), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and examples thereof include methyl, ethyl, propyl, butyl, etc., and methyl is preferred. A plurality of R2s may be the same or different. In formula (2), A, B, and n have the same meanings as A, B, and n in formula (1), as described above.

[0089] The polyorganosiloxane represented by formula (2) has a group represented by A-B at a single terminal, and it is preferable because it easily improves the dispersibility of the filler.

[0090] <Polyorganosiloxane represented by formula (3)>

[0091] The polyorganosiloxane according to one embodiment of the present invention has a structure represented by the following formula (3). This polyorganosiloxane has a group represented by A-B at both terminals.

[0092]

[0093] (In formula (3), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and A, B, and n have the same meanings as A, B, and n in formula (1).)

[0094] R2 in formula (3) has the same meaning as R2 in formula (2), and A, B, and n have the same meanings as A, B, and n in formula (1).

[0095] <Polyorganosiloxane represented by formula (4)>

[0096] The polyorganosiloxane according to one embodiment of the present invention has a structure represented by the following formula (4). This polyorganosiloxane has a group represented by A-B in the side chain.

[0097]

[0098] (In formula (4), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, m is an integer of 1 or more and 10 or less, and A, B, and n have the same meanings as A, B, and n in formula (1))

[0099] R2 in formula (4) has the same meaning as R2 in formula (2), and A, B, and n have the same meanings as A, B, and n in formula (1).

[0100] In formula (4), m is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 5 or less, and more preferably 1 or 2. If m is in such a range, the adsorptivity to the filler is improved and the fluidity is also improved, so it is preferable.

[0101] In addition, the polyorganosiloxane represented by formula (4) may be a random polymer or a block polymer. More specifically, the units shown in parentheses of m and the units shown in parentheses of n may exist in a block form or a random form in the molecule.

[0102] The above-mentioned polyorganosiloxane preferably has the structure shown in the above formula (2) or the above formula (3), and more preferably has the structure shown in the above formula (2). By having the structure shown in the above formula (2) or the above formula (3), the main chain of the above-mentioned polyorganosiloxane is not restricted by the filler and the configurational freedom becomes higher, so the excluded volume becomes larger. As a result, it is easy to further improve the dispersibility of the filler.

[0103] <Polyorganosiloxanes with other structures>

[0104] The polyorganosiloxane according to an embodiment of the present invention may have a structure with A-B at a single end as shown in the above formula (2) and also have A-B in the side chain as shown in the above formula (4). In addition, the polyorganosiloxane according to an embodiment of the present invention may have a structure with A-B at both ends as shown in the above formula (3) and also have A-B in the side chain as shown in the above formula (4). However, from the viewpoint of making it easier to improve the dispersibility of the filler, the above-mentioned polyorganosiloxane is most preferably a structure with A-B only at a single end as shown in the above formula (2).

[0105] <Manufacturing method of polyorganosiloxane>

[0106] The manufacturing method of the polyorganosiloxane of the present invention is not particularly limited, and it can be obtained by reacting a generally available polyorganosiloxane having a functional group with a compound having 3 or more and 6 or less conjugated aromatic 6-membered rings and having a functional group capable of reacting with the functional group of the above-mentioned polyorganosiloxane. If an example is given, the polyorganosiloxane of the present invention can be manufactured by the acetalization reaction of an aldehyde and a diol, the hydrosilylation reaction of a hydrosilyl group and a carbon-carbon unsaturated bond, etc.

[0107] For example, the polyorganosiloxane of the present invention can be manufactured by the reaction of a polyorganosiloxane having a diol structure with a compound having an aldehyde group and 3 or more and 6 or less conjugated aromatic 6-membered rings. As another method, the polyorganosiloxane of the present invention can be manufactured by the reaction of a polyorganosiloxane having a hydrosilyl group at the end and / or side chain with a compound having a group having a carbon-carbon unsaturated bond such as acryloyl or methacryloyl and 3 or more and 6 or less conjugated aromatic 6-membered rings.

[0108] <Filler>

[0109] The polyorganosiloxane of the present invention shown in the above formula (1) is suitable for use as a dispersant for fillers.

[0110] Examples of the types of fillers include metal oxides, metal nitrides, carbides, carbon-based materials, and metal hydroxides. Among them, the polyorganosiloxane of the present invention has a high effect of improving the dispersibility of fillers having a π-conjugated system. Therefore, as the filler, a filler having a π-conjugated system is preferred, and graphite is particularly preferred.

[0111] The average particle size of the filler is not particularly limited, but is preferably 0.1 μm or more and 250 μm or less, more preferably 0.2 μm or more and 100 μm or less.

[0112] In addition, the average particle size can be measured using a "laser diffraction particle size distribution measuring device" manufactured by Horiba, Ltd., and the particle size (d50) at a cumulative volume of 50% can be set as the average particle size.

[0113] By using the polyorganosiloxane of the present invention, the filler can be well dispersed in the solvent. The type of the solvent is not particularly limited as long as the polyorganosiloxane described in the present invention can be dissolved therein, and preferably, for example, toluene, cyclohexanone, methyl ethyl ketone, isopropyl alcohol, ethyl acetate, etc. The blending amount of the polyorganosiloxane represented by the formula (1) relative to 100 parts by mass of the filler is preferably 10 parts by mass or more, more preferably 100 parts by mass or more, further preferably 500 parts by mass or more, and preferably 10,000 parts by mass or less, more preferably 5,000 parts by mass or less, further preferably 2,000 parts by mass or less.

[0114] Examples

[0115] Hereinafter, the present invention will be clarified by giving specific examples and comparative examples of the present invention. In addition, the present invention is not limited to the following examples.

[0116] [Performance of Dispersant: Evaluation of Dispersibility]

[0117] 0.1 g of graphite (average particle size: 10 μm), 1 g of the polyorganosiloxane (dispersant) of each example and comparative example, and 10 g of toluene were subjected to ultrasonic treatment for 1 hour to disperse the graphite in toluene. Then, the sample was allowed to stand for 1 hour, and the dispersion state of the graphite was evaluated visually in four stages of AA to C.

[0118] AA: Completely dispersed

[0119] A: Half dispersed

[0120] B: Partially dispersed

[0121] C: Not dispersed and precipitated

[0122] [Viscosity of Polyorganosiloxane (Dispersant): Evaluation of Fluidity]

[0123] Using the E-type viscometer "TV-25" manufactured by Toki Sangyo Co., Ltd., the measurement was carried out at 25 °C, 50 rpm, and with a conical rotor "1°34’×R24", and the evaluation was conducted based on the following criteria.

[0124] AA: 200 mPa·s or less

[0125] A: More than 200 mPa·s and 300 mPa·s or less

[0126] B: More than 300 mPa·s and 400 mPa·s or less

[0127] C: More than 400 mPa·s

[0128] <Example 1>

[0129] 98.6 g of the organosiloxane compound having a 1,3-diol group represented by the formula (15) (n = 210), 1.4 g of 1-pyrenecarboxaldehyde as a monomer, 50 g of toluene as a solvent, and 0.6 g of a catalyst (manufactured by Organo Corporation, "Amberlyst15dry") were reacted at 100 °C for 24 hours under a nitrogen atmosphere. After the reaction, filtration was carried out using a 5.0 μm PTFE filter to remove the catalyst, and the filtrate was concentrated using a rotary evaporator and a vacuum dryer to obtain the polyorganosiloxane of Example 1. If the reaction formula is shown, it is as follows. In addition, the following reaction was confirmed by 1 1H NMR measurement. As the NMR measurement device, "ECX-400" manufactured by JEOL was used, and the measurement was carried out under the conditions of a sample concentration of 1 wt%, 25 °C, a measurement frequency of 400 MHz, and 8 cumulative times using deuterated chloroform as a solvent. Similarly for other examples and comparative examples, the progress of the reaction was confirmed by 1 1H NMR measurement.

[0130]

[0131] <Example 2>

[0132] The monomer was changed to 1.7 g of 3-perylenecarboxaldehyde, and synthesis was carried out in the same manner as in Example 1 to obtain the polyorganosiloxane of Example 2. If the reaction formula is shown, it is as follows.

[0133]

[0134] <Example 3>

[0135] The organosiloxane compound of formula (15) was changed to a compound with n = 70, and the amount of 1-pyrenecarboxaldehyde was changed to 4.2 g. Otherwise, the synthesis was carried out in the same manner as in Example 1, and the polyorganosiloxane of Example 3 was obtained. The reaction formula is omitted as it is the same as in Example 1 except that the compound of formula (15) is changed to a compound with n = 70.

[0136] <Example 4>

[0137] 98.6 g of a hydrogen-silyl group-containing organosiloxane compound (n = 70) represented by formula (16), 5.5 g of methyl acrylate (1-pyrene)methyl ester as a monomer, 50 g of toluene as a solvent, and 0.01 g of Karstedt catalyst (platinum-based catalyst) as a catalyst were reacted at 100 °C for 24 hours under a nitrogen atmosphere. Then, the reaction solution was concentrated using a rotary evaporator and a vacuum dryer to obtain the polyorganosiloxane of Example 4. If the reaction formula is shown, it is as follows.

[0138]

[0139] <Example 5>

[0140] The monomer was changed to 5.7 g of 2-(1-pyrene)ethyl acrylate. Otherwise, the operation was the same as in Example 4, and the polyorganosiloxane of Example 5 was obtained. If the reaction formula is shown, it is as follows.

[0141]

[0142] <Example 6>

[0143] The monomer was changed to 5.3 g of 1-pyrene acrylate. Otherwise, the operation was the same as in Example 4, and the polyorganosiloxane of Example 6 was obtained. If the reaction formula is shown, it is as follows.

[0144]

[0145] <Example 7>

[0146] 98.6 g of a hydrogen-silyl group-containing organosiloxane compound (n = 70) represented by formula (17), 11 g of methyl acrylate (1-pyrene)methyl ester as a monomer, 50 g of toluene as a solvent, and 0.01 g of Karstedt catalyst (platinum-based catalyst) as a catalyst were reacted at 100 °C for 24 hours under a nitrogen atmosphere. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer to obtain the polyorganosiloxane of Example 7. If the reaction formula is shown, it is as follows.

[0147]

[0148] <Example 8>

[0149] 98.6 g of a siloxane compound having a hydrosilyl group represented by the formula (18) (n = 70), 5.5 g of (1-pyrenyl)methyl methacrylate as a monomer, 50 g of toluene as a solvent, and 0.01 g of Karstedt catalyst (platinum-based catalyst) as a catalyst were reacted at 100 °C for 24 hours under a nitrogen atmosphere. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer to obtain the polyorganosiloxane of Example 8. If the reaction formula is shown, it is as follows.

[0150]

[0151] <Example 9>

[0152] 98.6 g of a siloxane compound having a hydrosilyl group represented by the formula (19) (n = 70), 22 g of (1-pyrenyl)methyl methacrylate as a monomer, 50 g of toluene as a solvent, and 0.01 g of Karstedt catalyst (platinum-based catalyst) as a catalyst were reacted at 100 °C for 24 hours under a nitrogen atmosphere. The reaction solution was concentrated using a rotary evaporator and a vacuum dryer to obtain the polyorganosiloxane of Example 9. If the reaction formula is shown, it is as follows.

[0153]

[0154] <Example 10>

[0155] The monomer was changed to 1.2 g of 9-anthracenecarbaldehyde, and otherwise, the same operation as in Example 1 was carried out to obtain the polyorganosiloxane of Example 10. If the reaction formula is shown, it is as follows.

[0156]

[0157] <Example 11>

[0158] The monomer was changed to 1.5 g of [1,1':4',1'']terphenyl-4-carbaldehyde, and otherwise, the same operation as in Example 1 was carried out to obtain the polyorganosiloxane of Example 11. If the reaction formula is shown, it is as follows.

[0159]

[0160] <Example 12>

[0161] The monomer was changed to 1.4 g of 1-pyreneacetaldehyde, and otherwise, the same operation as in Example 1 was carried out to obtain the polyorganosiloxane of Example 12. If the reaction formula is shown, it is as follows.

[0162]

[0163] <Example 13>

[0164] The monomer was changed to 5.1 g of 3-perylene carbaldehyde, and otherwise, the operation was the same as in Example 3 to obtain the polyorganosiloxane of Example 13. If the reaction formula is shown, it is as follows.

[0165]

[0166] <Comparative Example 1>

[0167] The monomer was changed to 0.97 g of 2-naphthaldehyde, and otherwise, the operation was the same as in Example 1 to obtain the polyorganosiloxane of Comparative Example 1. If the reaction formula is shown, it is as follows.

[0168]

[0169] <Comparative Example 2>

[0170] The monomer was changed to 2.0 g of 1-coronene carbaldehyde, and otherwise, the operation was the same as in Example 1 to obtain the polyorganosiloxane of Comparative Example 2. If the reaction formula is shown, it is as follows.

[0171]

[0172] <Comparative Example 3>

[0173] The monomer was changed to 5.9 g of 3-(1-pyrenyl)propyl methacrylate, and otherwise, the operation was the same as in Example 4 to obtain the polyorganosiloxane of Comparative Example 3. If the reaction formula is shown, it is as follows.

[0174]

[0175] <Comparative Example 4>

[0176] 9.7 g of an organosiloxane compound having a monoalcohol group represented by the formula (20) (n = 140), 0.3 g of 1-pyrene butyric acid as a monomer, 30 g of tetrahydrofuran as a solvent, 0.3 g of N,N'-dicyclohexylcarbodiimide and 0.1 g of N,N-dimethyl-4-aminopyridine as condensing agents were used. The reaction was carried out at 0 °C for 24 hours under a nitrogen atmosphere, and the reaction solution was concentrated by a rotary evaporator. After concentration, the precipitate was removed by centrifugation, and the supernatant was obtained as the polyorganosiloxane of Comparative Example 4. If the reaction formula is shown, it is as follows.

[0177]

[0178] <Comparative Example 5>

[0179] The monomer was changed to 3.8 g of 1-vinylpyrene, and otherwise, the operation was the same as in Example 4, and the polyorganosiloxane of Comparative Example 5 was obtained. If the reaction formula is shown, it is as follows.

[0180]

[0181] <Comparative Example 6>

[0182] The monomer was changed to 3.8 g of 1-vinylpyrene, and otherwise, the operation was the same as in Example 8, and the polyorganosiloxane of Comparative Example 6 was obtained. If the reaction formula is shown, it is as follows.

[0183]

[0184] <Comparative Example 7>

[0185] The monomer was changed to 15.3 g of 1-vinylpyrene, and otherwise, the operation was the same as in Example 9, and the polyorganosiloxane of Comparative Example 7 was obtained. If the reaction formula is shown, it is as follows.

[0186]

[0187] <Comparative Example 8>

[0188] Instead of the organosiloxane compound represented by the formula (20) used in Comparative Example 4, the organosiloxane compound represented by the following formula (21) (n = 140) was used, and otherwise, the operation was the same as in Comparative Example 4, and the polyorganosiloxane of Comparative Example 8 was obtained. If the reaction formula is shown, it is as follows.

[0189]

[0190] Table 1

[0191]

[0192] In each of the polyorganosiloxanes shown in the examples having 3 or more and 6 or less conjugated aromatic 6-membered rings and any one of the α-position atom, β-position atom, and γ-position atom bonded to the aromatic 6-membered ring being a heteroatom, both the evaluation of dispersibility and the evaluation of fluidity were good. In contrast, in the polyorganosiloxanes of each of the comparative examples that do not have 3 or more and 6 or less conjugated aromatic 6-membered rings, or that do not have heteroatoms at the α-position atom, β-position atom, and γ-position atom of the aromatic 6-membered ring, the result was that either the evaluation of dispersibility or the evaluation of fluidity was poor.

Claims

1. A polyorganosiloxane having a structure represented by the following formula (1), In formula (1), each R1 is independently a group represented by A-B or a monovalent hydrocarbon group having 1 to 4 carbon atoms, At least one of the plurality of R1s is a group represented by A-B, where A is a divalent organic group bonded to a silicon atom, and B has 3 or more and 6 or less conjugated aromatic 6-membered rings, Among the atoms constituting A, when the atom bonded to the aromatic 6-membered ring of B is defined as the α-position atom, the atom bonded to the α-position atom is defined as the β-position atom, and the atom bonded to the β-position atom other than the α-position atom is defined as the γ-position atom, any one of the α-position atom, β-position atom, and γ-position atom is a heteroatom, n is an integer of 1 or more.

2. The polyorganosiloxane according to claim 1, having a structure represented by the following formula (2), In formula (2), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and A, B, and n have the same meanings as A, B, and n in formula (1).

3. The polyorganosiloxane according to claim 1, having a structure represented by the following formula (3), In formula (3), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, and A, B, and n have the same meanings as A, B, and n in formula (1).

4. The polyorganosiloxane according to claim 1, having a structure represented by the following formula (4), In formula (4), R2 is a monovalent hydrocarbon group having 1 to 4 carbon atoms, m is an integer of 1 or more and 10 or less, and A, B, and n have the same meanings as A, B, and n in formula (1).

5. The polyorganosiloxane according to claim 4, wherein m is 1 or 2.

6. The polyorganosiloxane according to any one of claims 1 to 5, wherein B is a fused-ring compound.

7. The polyorganosiloxane according to claim 6, wherein B contains a pyrene substituent or a perylene substituent.

8. The polyorganosiloxane according to claim 7, wherein A has 10 or fewer carbon atoms.

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